Method of dehydrogenating butene



06L 7, 1947. c, HOLDER 2,428,624

METHOD OF DEHYDROGENATING BUTENE Filed Nov. 10, 1943 JUTAD/ENE To Put /1=/cA TION 3U TE Ni 3 TORA CE.

Patented Oct. 7, 1947 Clinton H. Holder, Cranford, N. J1, assignor to Standard Oil Development Company, a corporation of Delaware Application November 10, 1943, Serial No. 509,647

. Claims. (Cl. 260-680) The present invention relates to improvements in the art of dehydrogenating hydrocarbons, andmore particularly, relates to the art of dehydrogenating mono-oleflns and'compounds, such as alkylated aromatics.

The production of synthetic rubber or rubberlike material has necessitated for many of these new products, the'manufacture'of intermediates in larger quantities than they have heretofore been manufactured. These new intermediates include substances, such as butadiene, styrene, and the like. For example, a product known as 1 Buna-S is prepared by reacting together under amount of CO2 in the charge and to this end I admit CO2 or a COz-containing gas from line 2| into line I4.

While there are several methods of preparing I butadiene, one satisfactory method involves the dehydrogenation of butenesa A number of catalysts have been proposed for this reaction, including the oxides of the 1V, V and VI group of the periodic system usually supportedon a carrier, such as magnesium oxide or the like. However, oxide catalysts,- such as molybdenum oxide or chromium oxide, when used to dehydrogenate butadiene, are not as suitable as other types of suitable conditions of temperature and pressure,

butadiene and styrene. The production of butadiene in normal oil refining practice is not great and this particular intermediate is now being manufactured in special plants in greater quantity than heretofore and additional plants for making this material arein the process of construction. Similarly, styrene plants are also being expanded or new ones constructed in order to prepare this necessary intermediate for synthetic rubber.

In the accompanying drawing, I have shown diagrammatically, an apparatus in which a preferred embodiment of my invention may be carried into practical eifect.

Referring to the drawing, butene-2 is withdrawn from storage I through line II, thence heated in a furnace l2. perheated in superheater I5, withdrawn through line I1 and mixed in line I4 with preheated butene-2 withdrawn from heater l2. The mixture then passes into reactor I9 containing catalyst C, later identified. The catalyst is usually in the form of pills or pelletssupported on a screen or grid 20. The product containing butadiene is withdrawn at 22' and delivered to'a purification system (not shown) whereby after separation of water, the hydrocarbons are solvent extracted, distilled, etc., in known manner to produce the desired product. I have not shown a complete plant with all of its accessory equipment such as heat exchangers, flow meters, and the like, but only sufiicient to enable a complete understanding of my invention. Periodically the valve in line i l is closed and the catalyst is treated with steam to remove deposits. The novelty in my present invention relates to including a small Meanwhile, steam is suatmosphere or lower.

catalysts in that the former are sensitive to steam. This sensitivity ofthe oxide catalysts of the VI group element to steam is a disadvantage in their use because the dehydrogenation of butene to butadiene is an operation which is preferably carried out under low pressure. If attempts. are made to lower the partial pressure of thebutene with steam, a catalyst, such as chromium oxide, and the like, is affected by the steam and therefore the said steam cannot be used. Of course, it is possible to dehydrogenate butene in undiluted condition but this requires relatively low pressures, namely, of the order of one-eighth of an has been developed, as previously indicated, a catalyst which is not sensitive to steam. Thus, in the application of Kenneth K. Kearby, Serial No. 430,873, filed February 14, 1942, there is disclosed a catalyst consisting of a major portion of magnesium oxide, a'minor portion of an iron oxide, a stabilizer, such as copper oxide, and a promoter, such as K20. In the preparation of this catalyst the most practical form of potassium to include is 'the carbonate. A representative composition of the catalyst'is as follows:

- Per cent MgO F18201 K20 ...L."*I 5 CuO -L. 5

This catalyst under actual test has proved to be satisfactoryand to ,gi'vegood yields with high selectivity when used in thedehydrogenation of butene toform butadiene. A good way to operate the process is to dilute the butene feed going to he reactor with 8 or 10 volumesof steam and On the other hand, there Out #141119: 2% Q.

3 when the gas pressure in thereactor itself about 1 atmosphere, it will'be obvious that the partial pressure of the butene will be from oneeighth to one-tenth of an atmosphere. At this relatively low pressure dehydrogenation product may be formed.

It is characteristic of the mono-olefin dehydrogenation reaction that carbonaceous material deposits on the catalyst but this may be removed by steam at normal reactiontemperatures, this reaction being promoted by the presence of the potassium in the catalyst. Thus, it is customary to employ a cyclic procedure consisting of an hour reaction period while feeding both steam and hydrocarbon followed by. a regeneration period of the same duration in which only steam is fed. Typical operating conditions are. as follows:

Inlet temperature 1225 F., average reactor temperature 1150 F., average reactor pressure 8#/sq.-in. gauge, 200 volumes of butene/catalyst volume/hr., 2000 volumes of steam during dehydrogenation/catalyst vol./hr., and 500 volumes of steam during regeneration/catalyst vol./h'r. The complete cycle consists of acne-hour dehydrogenation and a one-hour regeneration period, the original catalyst containing. approximately 5%m0.

In operating this process as described above, however, it has been found that the catalyst loses potassium oxide by volatilization. Since the purpose of the potassium is to keep the catalyst v relatively free of coke by promoting the water gas reaction, it is obvious that the useful life of the catalyst will be greatly shortened by the accumulation of coke resulting from potassium losses.

The following analyses of samples representative of various positions in a catalyst'bed after 980 hours of operation illustrate how' the loss first occurs at the inlet and gradually works down through the bed. l

Vol. Per Cent 0! Total Bed K 0 in Sample 7 Cut #7-207; Cut #8 Outlet 13% Since it is apparent that the potassium car bonate in the catalyst is somewhat volatile, one' rather obvious means of combating this problem consists of placing a small quantity of potassium carbonate on the top of the catalyst or at'some Per Cent cipmtion of the volatile potassium compound by reconverting it .to the relatively non-volatile compound potassium carbonate.

I have found that the rate at which potassium is lost from the catalyst may be greatly reduced by including in the charge a, relatively small quantity of carbon dioxide, namely, 0.1 to 0.5%. The useful life of the catalyst may be consequently prolonged since by maintaining the original potassium concentration. in the catalyst by this means, the catalyst may be kept relatively Although K20 has a rather low vapor pressure at about 1200 F. the presence of the steam con- .verts this to KOH and consequently classifies this dissociation with the'type in which a solid dissociates to two volatile components. When this system is at equilibrium it will possess a definite value for the equilibrium constant, K1 which for the overallreaction-is represented as follows:

Since K1 and the denominator are constant at any one temperature, it follows that A where K2 is a constant. Hence, it is evident that control of the concentration of potassium in the vapor state may be obtained by adjusting the. 1 CO2 concentration and vice versa.

Or, in other words, the rate of loss of potassi'umfrom catapoint where the hot incoming feed gases contact the potassium carbonate. 'Another consists of injecting into the hot feed line a small quantity of a potassium compound such as the carbonate or the hydroxide, in liquid form as an aqueous solution or as molten hydroxide. Both of these methods depend on partially saturating the incoming stream with a volatilized potassium com;- pound thereby reducing the amount contributed by the catalyst. My experience has been that with each of these procedures plugging of the reactor occurred in short order due, presumably, to deposition of the potassium compound at some point in the reactor bed. Although this may not always occur, it is, however, an inherent. disad- 1 vantage. As will be evident later, this was prob- 3 ably the result of the partial pressure of the C02 produced-in the reaction zone which caused-pm lysts of the type described above may be, greatly retarded by adding a small amount of CO2 with the feed.

That the loss of potassium from catalysts con- A taining potassium carbonate does occur by the route described above is illustrated by the following evidence: 7 I 7 (1) I have found that the rate of volatilization of pure potassium carbonate in the presence of steam is much higher than the rate ,of loss of potassium from a catalyst during use, based on theanalyses of these used catalysts. For instance, they rate of potassium carbonate loss was 24 lbs/million cubic feet of steam when pills of this material were steamed at 12 50 F. whereas thef rate of loss found for a typical catalyst was 0.5

lb./million cubic feet of steam, or48-times slower than with steam. Presumably the CO2 produced in the reactor by the reaction of steam and the coke on the catalyst influenced the rate of loss of potassium from the catalyst considerably. It should be pointed out, however, that even though the CO2 concentration'is, as high ccur in the case of the I as about 1% at the reactor outlet during either dehydrogenationor regeneration, this is of no avail in regard to the catalyst at the very beginning of the reaction zone although it will decrease the rate of loss [of potassium loss from points further removed from the'inlet. The inlet portion of the bed is always exposedto COz-fIee gases and as the catalyst loses potassium and becomes coked, the point in the catalyst bed at which the reaction begins to occur is further removed from the inlet thus permitting potassium depletion to progress through the bed.

(2) The following table shows the effect of the nature of the gas when subjecting K2003 pills to a gas stream at 1400" F.

Temperature F 1400 Gas employed Steam Air N1 Gas rate-vols. STP/voL/hr 5450 2160 Partial press. of K100] in outlet stream oiHg 0.14 0.032 0.023 Pounds oi K Coilmillion c. i. of gas 67 15 11 The lower gas rate employed in the air and N2 experiments should permit a closer approach to saturation but on the other hand the apparent loss was only about /5 of that when using steam. Thus, with air and N2 it is believed the dissociation still does occur but the K20, which is relatively non-volatile, remains on the pills whereas in the presence of steam this oxide is converted.

'Iemperature F 1400 Steam rate-vols. STP/voL/ hr 4800 Per cent C01insteam. O 0.1 0.2 0.5 1.0 Partial pressure of K 0 utlet steam-mm. oi Hg. 0.050 0.027 0.017 0.0065 0.0016 Number of KiCOa/million c. i. of

steam 24 i3 810 3.1 0.76 Actual number of times loss rate was retarded com pared to rate without added O01 1. 2 2. 8 7. 7 31 0.1% of CO2 will almost double the length of time required to volatilize the K2003, for instance. The experimental work thus confirms the theory postulated above in which it was stated that the potassium concentration in the vapor'could be controlled by the CO2 partial pressure and consequently it is therefore possible to extend the life of catalysts of the type described herein several times by using the method described in this invention. When no provision is made for retarding potassium loss from the catalyst the useful life of such catalysts has been found to be of the order of 2000 hours (83 days). Furthermore, if one replenishes the catalyst with potassium, for instance, by preceding the bed with K2003 pills, it has been discovered that the 'catalyst activity is restored markedly and in fact approaches that of fresh catalyst while at the same time an unusually large amount of CO2 appeared in the outlet gases proving that the catalyst had become coked as it became deficient in potassium and that the catalyst was'otherwise in good condition.

A particularly good illustration of the benefit to be derived from the invention herein described lies in two runs which I have made under similar conditions and over the same catalyst, the chief diflerence being that in one run I purposely introduced CO2 into the reaction zone along with turning it to the reactor.

activity with a consequent loss of yields.

6 the feed while in the second case no CO: was added, in fact operation was similar to that which would be normally used by those familiar with the art.

Case I- O0: Added Case II- NO CO1 Added Hours of Operation.

Vol. Per Cent of Total Per Cent Vol. Per Cent of Total Bed 1 K10 Bed Cut #lA-Inlet 4.1%... 1 Cut aria- .4%.

- co wcnqoswrom sweep 7 Cut #6-0utlgt 18.8%.- Cut #1-2o% Gut #80utlet 13%..

I An analysis of the combined cut #1 showed 2.8%. The original catalyst contained apcproximately 6.5% K10. The separationin cut 1A and 1B was ma e based on color. The low per cent K10 pills of cut 1A were dark due to coke accumulation.

Approximately 1% CO2 by volume based on total charge was added over the first cycles after which it was reduced to 0.05%. It is evident that even with the rather low CO2 concentration employed in the greater part of this run the catalyst 10st considerably less K20 than it did when operated without CO2 addition.

The main object of my invention, therefore, is to carry out the dehydrogenation of .a monooleiin or an alkylated'aromatic using a catalyst containing a volatile compound of potassium serving as a promoter, under such conditions as to prevent the loss of the said volatile potassium compound by volatilization. I have found it best to employ 0.1 to 0.5 vol. C02 with the charge and under such conditions the catalyst life will be extended to 2-5 times its useful life when C02 addition is not employed. In fact, when using CO2 the catalyst life is usually terminated for some reason other than thatit has lost potassium.

The foregoing examples are purely illustrative of my invention and do not impose any limitation thereon. For instance, it is intended that alkali metal carbonates in general be included in this invention and that such carbonates may be incorporated in various catalysts, such as those used for aromatization as well as those used for dehydrogenation.

The method employed to supply CO: to the reaction zone may vary depending on the particular circumstances. For instance one may burn a portion of the butene feed in order to generate the necessary CO2.

scrubbing CO: from the product gases and re- In operating this process, however, it-has been found that the catalyst loses potassium oxide by volatillzation and this results in the lowering of The most practical form of potassium compound to include in the catalyst composition is potassium carbonate in the presence of steam which is added with the charge. The carbonate at the high temperatures of reaction is converted to hydroxide and this material is more volatile than the carbonate and the oxide and hence is carried off with the reaction products. It is to repress oxide or hydroxide formation that I add CO2, for this addition tends to shift the equilibrium toward forming the least volatile compound of the three, viz., the carbonate.

Per Cent Another method consists of" diene. I

What I claim is 1. The method of dehydrogenating butene-2 which comprises forcing a mixture 01' steam and butene-2, and CO: in an amount representing a small fraction of the total charge through a bed of catalyst consisting of MgO, F6203, and K200: in a reaction zone, at elevated dehydrogenation temperatures but at a partial pressure of the butene-2 below atmospheric pressure, and recovering a product containing butadiene from said reaction.

2. The method of dehydrogenating butene which, comprises charging a preheated mixture of steamand butene to a reaction zone containing a catalyst consisting essentially of MgO, FezOa, .a stabilizer and a volatile alkali metal compound, maintaining the reactant at dehydrogenating temperatures and prolonging the activity of'the catalyst by adding an "amount of .Ca representing a small fraction of the total the stabicharged under dehydrogenation conditions to a steam-resisting dehydrogenation catalyst containing a metal compound which is volatilizable under the reaction conditions and which forms a carbonate oi. relatively low volatility, wherein steam is used to reduce the partial pressure of the hydrocarbons during the. dehydrogenation reaction, the improvement which comprises charging to the catalyst during the dehydrogenation reaction an amount of CO2 representing a small fraction of the total charge to the catalyst but being sufficient-to maintain said metal compound in the form of said carbonate of low volatility.

7. The method of claim 6 in which said metal compound is an alkali metal compound selected from the group consisting of alkali metal oxides and carbonates.

8. The method of claim 6 in which the CO2 is not over 1% by volume of the total charge to thereaction zone, the hydrocarbon is butene-2 and the product 01 the dehydrogenation is buta- 9. The process or the method of claim 6 in which the metal compound is KzCOs.

10. In the dehydrogenation of an olefin in the presence of a steam-resisting dehydrogenation catalyst containing an active dehydrogenation oxide catalyst, a stabilizer and a promote;- on a magnesium oxide carrier the promoter being originally a volatile alkali metal carbonate forming volatile products under reaction conditions wherein steam is used to reduce the partial pressure of the hydrocarbons during their dehydrogenation in a reaction zone, the improvement comprising charging to the reaction zone, which contains the catalyst, a total feed stock charge of an olefin and steam containing C02 in an amount representing a small fraction of the total charge but adequate for repressing loss of the promoter, maintaining the feed stock in contact with the catalyst at elevated temperatures and at a relativelylow partial pressure of the'said olefin for a sufiicient period of time to effect the desired dehydrogenation of the hydrocarbons, and withdrawing reaction products from' said reaction zone.

11. The method of claim 10 in which the CO: is not over 1% by volume of the total charge to the reaction zone, the olefin, is butene-2 and the product butadiene.

12. The method of claim 10 moter is KzCOa.

13. The method of dehydrogenating hydrocarbons in the presence of a steam-resisting catalyst containing anactive dehydrogenation iron oxide component a stabilizer, and a minor amount of a promoter consisting of an alkali metal carbonate, which comprises maintaining the pro-' motor 'as a carbonate by adding to a reaction charge of hydrocarbons and steam that contacts said catalyst during dehydrogenation of the hydrocarbons an amount of carbon dioxid that represents a small fraction of'the total reaction in which the procharge and which prevents dissociation of the alkali metal carbonate. v

14. The method of dehydrogenating hydrocarbons in the presence of a steam-resisting active hydrocarbon material, which comprises introducing into contact with said catalyst a sufficient quantity of added carbon dioxide to decrease loss 01' the potassium carbonate from the catalyst by dissociation and volatilization. I

j ,CLINTON H. HOLDER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,732,381 Schmidt et a1. Oct. 22, 1929' 2,148,140 -Tropsch Feb. 21, 1939 2,211,219 Thacker Aug. 13, 1940 2,315,107 Chickinofi et a1. Mar. 30, 1943 2,367,620 Schulze et a1. Jan. 16, 1945 2,391,646 Schulze et a1. Dec. 25, 1945 

